Compatibility agent and method

ABSTRACT

A compatibility agent comprising a block copolymer of ethylene oxide and propylene oxide comprising about 30-80% ethylene oxide and about 20-70% propylene oxide which has been found useful for making pesticidal compositions compatible when combined.

TECHNICAL FIELD

The present invention relates to a compatibility agent, moreparticularly to a compatibility agent which renders compatible a mixtureof formulated pesticidal compositions, wherein at least one formulatedpesticidal composition contains an anionic surfactant, and at least oneformulated pesticidal composition contains a cationic surfactant.

BACKGROUND AND PRIOR ART

Farmers find it desirable to tank mix formulated commercial herbicidesin the field. The reasons for this desirability may include a need toenhance efficacy through a synergistic response, or the desire tocontrol different kinds of weeds. In addition, mixing formulatedherbicides may allow greater weed control, while overall using lessactive ingredients. Further, it might be desirable to tank mix aformulated insecticide, or other pesticides, with a formulatedherbicide. In short, the greater flexibility to tank mix formulatedproducts, the more ability a farmer has to adapt available resources tocombat new and existing problems.

Formulated pesticidal mixtures comprising two different activeingredients, wherein one of the commercial formulations contain acationic surfactant and the other contains an anionic surfactant, canpresent a special problem. Sometimes said mixtures result in formationof a precipitate or sediment due to the incompatibility of thesurfactants. The resulting precipitates make spraying the mixtures quiteproblematic. Agglomerated mixtures do not flow properly, and tend toclog spray rigs, hoses and nozzles. The term pesticide may includeherbicide, insecticide, fungicide or biocide.

U.S. Pat. No. 4,446,042 describes an invention which relates to laundrydetergent compositions containing nonionic surfactants, quaternaryammonium cationic surfactants and selected anionic brighteners. Theselection of suitable brighteners for detergents containing nonionic andcationic surfactants is problematic since many conventional brightenersare anionic in nature and tend to form insoluble complexes with thequaternary ammonium cationic surfactants. This surfactant compatibilityproblem is discussed and solved with certain stilbene disulfonateanionic brighteners.

Another area where this type of compatibility problem exists is in thearea of dyeing or printing. In U.S. Pat. No. 4,270,916 cationic orcertain anionic dyes are rendered compatible with normally incompatibleanionic polymers by the addition of nonionic, amphoteric or anionicsurface active agents. Examples of such polymers are algin, xanthan gum,S-7 gum polyacrylic acid or polymethacrylic acid. Among the varioustypes of nonionic detergents are condensation products of ethylene oxidewith fatty acids, condensation products of ethylene oxide with fattyalcohols, condensation products of ethylene oxide with fatty amines orfatty amides and condensation products of ethylene oxide with phenoliccompounds. Among the various anionic surfactants are aliphatic fattycondensate with ethylene oxide, the sodium salt of oleyl sarcoside andcondensation product of fatty acids and proteins.

U.S. Pat. No. 4,966,728 relates to adjuvants for postemergent herbicideswhich are crop oil concentrates. The crop oil concentrates of thatinvention enhance the activity obtained with other commercial adjuvants.The adjuvant mixtures are suitable for cyclohexanone-type herbicides.The crop oil concentrates of that invention comprise, a mixture of: a) afirst active component which is a low foaming nonionic surfactant; b) ananionic surfactant derived from esterification of a polyoxyalkylenenonionic surfactant with a dihydric or trihydric inorganic acid or bycarboxylation with an organic acid derivative; and c) optionally a thirdactive component which is a lower alkanol ester of a long chain fattyacid and d) a fourth component of a hydrocarbon "oil".

U.S. Pat. No. 5,084,087 describes an invention relating to adjuvants forpostemergent herbicides which fall into the category of crop oilconcentrates. The crop oil concentrates of that invention comprise amixture of: a) one or more herbicides selected from the group consistingof diphenylether herbicides, phenoxyphenoxy herbicides, imidazolineherbicides and cyclohexenone herbicides b) an emulsifier component whichis a combination of (i) a polyoxyalkylene nonionic surfactant having anHLB of from 10 to 14 and (ii) an anionic surfactant selected from thegroup consisting of the dialkyl metal sulfosuccinates and the metalalkylbenzene sulphonates; c) optionally a second surface activecomponent which is a low foaming polyoxyalkylene nonionic surfactanthaving an HLB of less than 10; and d) a lower alkanol ester of a longchain fatty acid. As an additional component, a hydrocarbon oil may beadded.

The present invention relates to the addition of a nonionic surfactant,also called a compatibility agent, which renders compatible mixtures ofnormally incompatible formulated pesticides, preferably herbicides. Itis an object of the present invention to provide an agent for makingcombined pesticidal compositions compatible, said composition comprisingat least one formulated pesticidal composition containing a cationicsurfactant, and at least one formulated pesticidal compositioncontaining an anionic surfactant. Another object of the presentinvention is to prevent the formation of a precipitate or sediment inmixtures of pesticides containing cationic and anionic surfactantsnormally incompatible with each other. A further object is to provide astable pesticidal mixture containing at least one cationic surfactantand at least one anionic surfactant. A still further object of thepresent invention is a method of controlling undesirable vegetation withsaid combined compatible pesticidal compositions.

SUMMARY OF INVENTION

One aspect of this invention relates to a compatibility agent whichrenders compatible, mixtures of normally incompatible formulatedpesticides, and more specifically, the use of a compatibility agentcomprising:

a block copolymer of ethylene oxide and propylene oxide comprising about30-80% ethylene oxide and about 20-70% propylene oxide. In one aspectthis invention comprises a compatibility agent comprising:

a) a block copolymer of ethylene oxide and propylene oxide comprisingabout 30-80% ethylene oxide and about 20-70% propylene oxide;

b) an antifoaming agent; and

c) an antifreeze agent.

Another aspect of this invention relates to a pesticidal compositionwherein the compatibility agent and more particularly the blockcopolymer component of it is combined with, or incorporated into, apesticidal composition containing an anionic or cationic surfactant.

In still another aspect, this invention relates to a combined pesticidalcomposition, comprising:

a) a block copolymer of ethylene oxide and propylene oxide comprisingabout 30-80% ethylene oxide and about 20-70% propylene oxide;

b) a first formulated pesticidal composition containing a cationicsurfactant; and

c) a second formulated pesticidal composition containing an anionicsurfactant.

DETAILED DESCRIPTION OF THE INVENTION

It has now been found that combined formulated pesticidal compositions,preferably herbicidal compositions, comprising at least one formulatedpesticidal composition having a cationic surfactant, and at least oneformulated composition having an anionic surfactant, that are normallyincompatible with each other, are rendered compatible by the presence ofa nonionic surfactant. In general, pesticidal active ingredients are notapplied to the locus of the pests alone. Normally these activeingredients are applied in combination with surface active agents,wetting agents, solvents, oils, carriers or diluents or mixturesthereof. The term "formulated pesticidal compositions" refers tocompositions containing an active ingredient(s) and one or more of theseother inert ingredients.

In some aspects of this invention, the compatibility agent will becombined with, or incorporated into a formulated pesticidal compositioncontaining the cationic or anionic surfactant. In other aspects, thecompatibility agent will be separate in order that it may be used intank mixes in the field. In still other aspects of the invention, thecompatibility agent may be combined with formulated pesticidalcompositions containing cationic, nonionic or amphoteric surfactants ormixtures thereof.

It has now been surprisingly found that certain nonionic surfactants actas effective compatibility agents of combined pesticidal compositions.The nonionic surfactants useful as compatibility agents are nonionicwater soluble block copolymers of ethylene oxide and propylene oxide.These surfactants have about 30-80% ethylene oxide and about 20-70%propylene oxide content, preferably about 30-50% ethylene oxide andabout 50-70% propylene oxide content, and most preferably about 70%ethylene oxide and about 30% propylene oxide content. The averagemolecular weight is between 5000-15,000 g/mole, preferably about between4900 to 6500 g/mole, and most preferably about 12,000-13,000 g/mole. Thehydrophile-lipophile balance (HLB) is about 7 to 23, preferably 7-18,and most preferably 18-23. The preferred nonionic surfactants acting ascompatibility agents are Pluronic P-103®, Pluronic P-104®, PluronicP-105®, Pluronic F-108® and Pluronic F-127®, which are available fromBASF.

CATIONIC SURFACTANTS

Among the various cationic surfactants which are rendered compatiblewith anionic surfactants, with the addition of the nonioniccompatibility agent of this invention, include ethoxylates of tallowamine. The term "tallow" refers to alkyl groups derived from tallowfatty acids. Other cationic surfactants are Ethoquad C/25, which may bedescribed as methylpolyoxyethylene (15) coco-ammonium chloride, EthoquadC/12, which may be described as methylbis(2-hydroxyethyl) coco-ammoniumchloride, and Duoquad T-50, which may be described as a diquaternaryammonium salt, all available from Akzo Chemie America. The term "coco"refers to alkyl groups derived from coconut fatty acids. This list isnot intended to be exhaustive, but other cationic surfactants will beapparent to those skilled in the art.

A commercial herbicide containing a cationic surfactant, made compatiblewith various anionic surfactants by the compatibility agent of thisinvention is Roundup®. The active ingredient in Roundup® isN-phosphonomethylglycine isopropylamine salt. It is available fromMonsanto Co.

ANIONIC SURFACTANTS

Among the anionic surfactants which have been found compatible with theabove cationic surfactants using the compatibility agent, are alkylarylsulfonate salts, preferably the calcium salts, although the alkali metalsalts and other alkaline earth metal salts may be used. Most preferredis calcium dodecylbenzene sulfonate. A commercial herbicide containingan alkylbenzene sulfonate salt surfactant is Surpass®-100, availablefrom Zeneca Agrochemicals. The active ingredient in Surpass®-100 is2-chloro-N-ethoxymethyl-6-ethylacet-o-toluidide, commonly known asacetochlor.

Acetochlor is a member of the acetanilide class of herbicides. Alachloris another acetanilide herbicide. Other acetanilide herbicides are knownto those skilled in the art.

OPTIONAL COMPONENTS

In addition to the nonionic surfactant, there are other ingredientswhich may be added to affect different properties of the compatibilityagent. For instance, an antifoaming or defoaming agent may be added.Nonionic surfactants which are block copolymers may be used asantifoaming agents. A preferred antifoaming agent is Pluronic L-61®.Pluronic L-61® is a block copolymer of ethylene oxide and propyleneoxide available from BASF. The propylene oxide content is approximately10%.

In addition to antifoaming agents, antifreeze agents such as propyleneglycol, ethylene glycol, isopropyl alcohol, urea ammonium nitrate andother salts. This list is not meant to be exhaustive, but those skilledin the art will know of other freezing point depressants.

Further, biocides may be included to prevent the degradation of thesurfactants by microbes. The Proxel® series are typical examples ofsuitable biocides and they are available from ICI Americas. Otherbiocides will be known to those skilled in the art.

COMPATIBILITY TEST

The test used to establish compatibility may be performed in a graduatedcylinder. This test involves mixing the components in the followingorder: a formulated pesticidal composition containing an anionicsurfactant, the compatibility agent and finally a formulated pesticidalcomposition containing a cationic surfactant. The cylinder is invertedseveral times to agitate and mix the ingredients.

An acceptable result in the graduated cylinder test is evidenced by theabsence of flocculation or sediment, or if flocculation or sediment ispresent it must be capable of being easily dispersed upon agitation ormixing. Flocculation which results in a hard pack sediment or softflocculation which agglomerates will give unacceptable results.Solutions where there is neither flocculation nor sediment, or solutionswhere the flocculation is easily dispersed are poured through a 100 meshsieve. To be acceptable, there must be little or no residue present whenthe solution is passed through the sieve. Mixtures which leave little orno residue on the sieve are subjected to a more rigorous tank mix testwith a three gallon spray rig.

The three gallon spray rig is composed of a square tank with a threegallon capacity. The tank is fitted with a recirculation pump whichdraws fluid from the bottom center of the tank. The inlet for the tankis a "t-shaped" nozzle located in the center of the tank approximatelyone inch from the bottom which provides agitation for the solution. Therecirculation pump is fitted with a pressure regulator, a 50 meshin-line screen and a spray nozzle.

The procedure for conducting a tank mix test in the three gallon rig isto first add water to the one and one half gallon level and start therecirculation. The pressure regulator is adjusted to 45-50 psi. Atrazineis added to the tank and allowed to disperse completely, which typicallytakes 30-60 seconds. Next, the formulated pesticidal product containingan anionic surfactant, such as Surpass®-100, is added and allowed todisperse completely. This typically takes 30-60 seconds. Thecompatibility agent is then added and allowed to disperse completely.This usually takes 30-60 seconds. Any remaining tank mix components areadded, with the order of addition generally not being important. Wateris added to the three gallon level and the solution is allowed torecirculate for 10 minutes. The recirculation is stopped and thesolution is allowed to stand undisturbed for 20 minutes. The level offlocculation or sediment is noted and the contents recirculated for 10additional minutes. If flocculation or sediment is observed, the easewith which it disperses is noted. The solution is then sprayed through acommon spray nozzle and screen into a holding vessel.

The inside of the tank is inspected for residue on the sides and bottom.The 50 mesh in-line sieve is inspected for residue and the spray nozzleis disassembled and inspected for residue. A showing of trace amounts ofresidue on the inside of the tank, the in-line sieve, or the spraynozzle is indicative of a satisfactory result. The solution in theholding vessel is returned to the tank and allowed to stand for 2 hours.The inspection procedure is repeated and noted. The solution is allowedto stand undisturbed overnight. Little or no residue on the inside ofthe tank is indicative of a satisfactory result.

The following nonlimiting examples illustrate the present invention:

EXAMPLE 1

A two-gallon nonionic compatibility solution for the three-gallon spayrig was prepared using the following ingredients which were mixed in theorder indicated:

    ______________________________________                                        Ingredient Weight % Weight (grams)                                                                            Order of Addition                             ______________________________________                                        Pluronic F-127 ®                                                                     10%       750.0      4                                             Pluronic L-61 ®                                                                      0.5%      37.5       3                                             Propylene glycol                                                                         15%       1125.0     2                                             water      74.5%     5587.5     1                                             ______________________________________                                    

The ingredients were mixed in a one-half gallon glass jug and combinedenough times to obtain two gallons total. The solution was heated toabout 50° C. and allowed to stir until the Pluronic F-127® wascompletely dissolved. This procedure was repeated until a total of twogallons was present. The above compatibility reagent was added to thefollowing combination of ingredients in the following order:

    ______________________________________                                        Ingredient     Amount     Order of Addition                                   ______________________________________                                        Atrazine-90 DF 120    grams   1                                               100pass ®  902    mL      2                                               Compatibility Agent                                                                          45     mL      3                                               Ambush ® 2-E                                                                             53     mL      4                                               Weedone-638 ®                                                                            53     mL      5                                               Roundup ®  141    mL      6                                               ______________________________________                                    

Ambush® is a trademark for permethrin available from Zeneca Ag Products.Atrazine-90 DF is a water dispersible granule available from Sostram.The mixture in the above example did not precipitate or agglomerate, andgave satisfactory results in the three-gallon spray rig.

EXAMPLE 2

The compatibility agent in Example 1 was used to make compatible thefollowing normally incompatible mixture. The ingredients were added inthe following order to a graduated cylinder:

    ______________________________________                                        Ingredient      Amount   Order of Addition                                    ______________________________________                                        100pass ®   6.5    mL    1                                                Compatibility Agent                                                                           0.4    mL    2                                                Weedone-638 ®                                                                             0.48   mL    3                                                ______________________________________                                    

Weedone-638® is a commercial herbicidal product, the active ingredientof which is 2,4 dichlorophenoxyacetic acid; it is available fromRhone-Poulenc Agrochimie. The mixture in the above example did notprecipitate or agglomerate.

EXAMPLE 3

The compatibility agent in Example 1 was used to make compatible thefollowing normally incompatible mixture. The ingredients were added inthe following order into the three gallon spray rig:

    ______________________________________                                        Ingredient     Amount     Order of Addition                                   ______________________________________                                        DoublePlay ™                                                                              851    mL      3                                               Compatibility Agent                                                                          29     mL      2                                               Bladex ®   302    grams   1                                               ______________________________________                                    

The mixture in the above example did not precipitate or agglomerate.Bladex®, which is available from DuPont, is a commercial formulation of2-4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl!amino!-2-methylpropionitrile,commonly known as cyanazine. DoublePlay™ is a commercial herbicideavailable from Zeneca Agrochemicals. The active ingredients inDoublePlay™ are S-ethyl dipropylthiocarbamate, commonly known as EPTCand acetochlor. DoublePlay™ contains the surfactant AL2757, availablefrom ICI Americas Inc.

EXAMPLE 4

This example compares the results of a solution without the addition ofa compatibility agent (Part A) versus a solution with the addition of acompatibility agent (Part B).

Part A

To a graduated cylinder was added 7.48 grams Surpass®-100 dissolved in90 mL of water followed by 0.2 grams of Ethoquad C/25. The mixture wasdispersed completely. The cylinder was allowed to stand for 30 minutes.Flocculation and sedimentation were noted and re-dispersed. The contentsof the cylinder were then passed through a 100 mesh sieve.

    ______________________________________                                        Ingredient    Amount     Order of Addition                                    ______________________________________                                        100pass ® 7.48   grams   2                                                Water         90     mL      1                                                Ethoquad C/25 0.2    grams   3                                                ______________________________________                                    

Without the addition of a compatibility agent, 15 mL of flocculateappeared at the top and 15 mL of flocculate appeared at the bottom (30mL total) and a major sediment was left on the 100 mesh sieve.

Part B

To a graduated cylinder was added 7.48 grams Surpass®-100 dissolved in90 mL of water followed by the addition of the compatibility agent inExample 1 (0.44 grams) and finally 0.2 grams of Ethoquad C/25. Themixture was dispersed completely. The cylinder was allowed to stand for30 minutes. Flocculation and sedimentation were noted and re-dispersed.The contents of the cylinder were then passed through a 100 mesh sieve.

    ______________________________________                                        Ingredient     Amount     Order of Addition                                   ______________________________________                                        100pass ®  7.48   grams   2                                               Water          90     mL      1                                               Compatibility Agent                                                                          0.44   grams   3                                               Ethoquad C/25  0.2    grams   4                                               ______________________________________                                    

With the addition of the compatibility agent in Example 1 there appeared15 mL of flocculate at the top of the cylinder which readily disperses.No flocculate appeared at the bottom of the cylinder and a very minoramount of sediment on the 100 mesh sieve.

EXAMPLE 5

To a graduated cylinder was added 7.48 grams Surpass®-100 dissolved in90 mL of water followed by the addition of 0.44 grams of a compatibilityagent. The mixture was completely dispersed and then 0.2 grams ofEthoquad C/25 was added. The mixture was again dispersed completely. Thecylinder was allowed to stand for 30 minutes. Flocculation andsedimentation were noted and re-dispersed. The contents of the cylinderwere then passed through a 100 mesh sieve.

    ______________________________________                                        Ingredient     Amount     Order of Addition                                   ______________________________________                                        100pass ®  7.48   grams   2                                               Water          90     mL      1                                               Compatibility Agent                                                                          0.44   grams   3                                               Ethoquad C/25  0.2    grams   4                                               ______________________________________                                    

The compatibility agent comprised 10% by weight Pluronic P-103®, 0.5% byweight Pluronic L-61®, 15% by weight Propylene glycol, and 74.5% byweight water. There appeared 3 mL of flocculate at the top of thecylinder which readily disperses, no flocculate at the bottom and aminor amount of sediment on the 100 mesh sieve.

EXAMPLE 6

To a graduated cylinder was added 7.48 grams Surpass®-100 dissolved in90 mL of water followed by the addition of 0.44 grams of a compatibilityagent. The mixture was completely dispersed and then 0.2 grams ofEthoquad C/25 was added. The mixture was again dispersed completely. Thecylinder was allowed to stand for 30 minutes. Flocculation andsedimentation were noted and re-dispersed. The contents of the cylinderwere then passed through a 100 mesh sieve.

    ______________________________________                                        Ingredient     Amount     Order of Addition                                   ______________________________________                                        100pass ®  7.48   grams   2                                               Water          90     mL      1                                               Compatibility Agent                                                                          0.44   grams   3                                               Ethoquad C/25  0.2    grams   4                                               ______________________________________                                    

The compatibility agent comprised, 10% by weight Pluronic P-104®, 0.5%by weight Pluronic L-61®, 15% by weight Propylene glycol, and 74.5% byweight water. There was no flocculate at the top or bottom of thecylinder and a minor amount of sediment on the 100 mesh sieve.

EXAMPLE 7

To a graduated cylinder was added 7.48 grams Surpass®-100 dissolved in90 mL of water followed by the addition of 0.44 grams of a compatibilityagent. The mixture was completely dispersed and then 0.2 grams ofEthoquad C/25 was added. The mixture was again dispersed completely. Thecylinder was allowed to stand for 30 minutes. Flocculation andsedimentation were noted and re-dispersed. The contents of the cylinderwere then passed through a 100 mesh sieve.

    ______________________________________                                        Ingredient     Amount     Order of Addition                                   ______________________________________                                        100pass ®  7.48   grams   2                                               Water          90     mL      1                                               Compatibility Agent                                                                          0.44   grams   3                                               Ethoquad C/25  0.2    grams   4                                               ______________________________________                                    

The compatibility agent comprised, 10% by weight Pluronic P-105®, 0.5%by weight Pluronic L-61®, 15% by weight Propylene glycol, and 74.5% byweight water. There was no flocculate at the top or bottom of thecylinder and a minor amount of sediment on the 100 mesh sieve.

What is claimed is:
 1. A combined pesticidal composition comprising:a) ablock copolymer of ethylene oxide and propylene oxide comprising about30-80% ethylene oxide and about 20-70% propylene oxide; b) a firstformulated pesticidal composition containing a cationic surfactant; c) asecond formulated pesticidal composition containing an anionicsurfactant; wherein said first and second pesticidal compositions areincompatible in the absence of said block copolymer and compatible inthe presence of said block copolymer.
 2. A combined pesticidalcomposition according to claim 1, wherein said block copolymer ofethylene oxide and propylene oxide comprises about 30-50% ethylene oxideand about 50-70% propylene oxide.
 3. A combined pesticidal compositionaccording to claim 1, wherein said block copolymer of ethylene oxide andpropylene oxide comprises about 70% ethylene oxide and about 30%propylene oxide.
 4. A combined pesticidal composition according to claim1, wherein said first formulated pesticidal composition comprises anherbicide.
 5. A combined pesticide composition according to claim 1,wherein said second formulated pesticidal composition comprises anherbicide.
 6. A combined pesticidal composition according to claim 4,wherein said herbicide comprises an N-phosphonomethylglycine salt.
 7. Acombined pesticidal composition according to claim 5, wherein saidherbicide comprises an acetanilide.
 8. A combined pesticidal compositionaccording to claim 7, wherein said acetanilide comprises acetochlor. 9.A combined pesticidal composition according to claim 1, wherein thecomposition is a liquid.
 10. A method for controlling undesirablevegetation, comprising: applying to said vegetation or the locusthereof, a pesticidal effective amount of a composition according claim1.